Electrophoretic particles and processes for the production thereof

ABSTRACT

Polymer shells similar to those described in U.S. Pat. No. 6,822,782 can be formed on pigment particles by (a) physi-sorping a reagent comprising polymerizable groups on to the pigment particles by treating the particle with a reagent having a polymerizable or polymerization-initiating group, such that the reagent will not desorb from the particle surface when the particle is placed in a hydrocarbon medium; or (b) treating pigment particles bearing nucleophilic groups with a reagent having a polymerizable or polymerization-initiating group, and an electrophilic group, thus attaching the polymerizable or polymerization-initiating groups to the particle surface. The zeta potential of the pigment particles can be varied by a process similar to (b) but using a reagent which does not have a polymerizable or polymerization-initiating group.

REFERENCE TO RELATED APPLICATIONS

This application claims benefit of copending Application Ser. No.61/936,393, filed Feb. 6, 2014.

This application is also related to:

-   -   (a) U.S. Pat. No. 6,822,782;    -   (b) U.S. Pat. No. 7,411,720;    -   (c) U.S. Pat. No. 8,582,196;    -   (d) U.S. Patent Application Publication No. 2009/0009852 (now        abandoned); and    -   (e) U.S. Patent Application Publication No. 2014/0340430.

The entire contents of these patents and applications, and of all otherU.S. patents and published and copending applications mentioned below,are herein incorporated by reference.

BACKGROUND OF INVENTION

This invention relates to electrophoretic particles and processes forthe production thereof. More specifically, this invention relates tosurface modification of electrophoretic particles for the purpose, interalia, of controlling the charges on the electrophoretic particles whenthey are present with other components typically present inelectrophoretic media.

The terms “bistable” and “bistability” are used herein in theirconventional meaning in the art to refer to displays comprising displayelements having first and second display states differing in at leastone optical property, and such that after any given element has beendriven, by means of an addressing pulse of finite duration, to assumeeither its first or second display state, after the addressing pulse hasterminated, that state will persist for at least several times, forexample at least four times, the minimum duration of the addressingpulse required to change the state of the display element. It is shownin U.S. Pat. No. 7,170,670 that some particle-based electrophoreticdisplays capable of gray scale are stable not only in their extremeblack and white states but also in their intermediate gray states, andthe same is true of some other types of electro-optic displays. Thistype of display is properly called “multi-stable” rather than bistable,although for convenience the term “bistable” may be used herein to coverboth bistable and multi-stable displays.

Electrophoretic displays have been the subject of intense research anddevelopment for a number of years. Electrophoretic displays can haveattributes of good brightness and contrast, wide viewing angles, statebistability, and low power consumption when compared with liquid crystaldisplays. Nevertheless, problems with the long-term image quality ofthese displays have prevented their widespread usage. For example,particles that make up electrophoretic displays tend to settle,resulting in inadequate service-life for these displays.

Electrophoretic media require the presence of a fluid. In most prior artelectrophoretic media, this fluid is a liquid, but electrophoretic mediacan be produced using gaseous fluids; see, for example, Kitamura, T., etal., “Electrical toner movement for electronic paper-like display”, IDWJapan, 2001, Paper HCS1-1, and Yamaguchi, Y., et al., “Toner displayusing insulative particles charged triboelectrically”, IDW Japan, 2001,Paper AMD4-4). See also U.S. Pat. Nos. 7,321,459 and 7,236,291. Suchgas-based electrophoretic media appear to be susceptible to the sametypes of problems due to particle settling as liquid-basedelectrophoretic media, when the media are used in an orientation whichpermits such settling, for example in a sign where the medium isdisposed in a vertical plane. Indeed, particle settling appears to be amore serious problem in gas-based electrophoretic media than inliquid-based ones, since the lower viscosity of gaseous suspendingfluids as compared with liquid ones allows more rapid settling of theelectrophoretic particles.

Numerous patents and applications assigned to or in the names of theMassachusetts Institute of Technology (MIT) and E Ink Corporationdescribe various technologies used in encapsulated electrophoretic andother electro-optic media. Such encapsulated media comprise numeroussmall capsules, each of which itself comprises an internal phasecontaining electrophoretically-mobile particles in a fluid medium, and acapsule wall surrounding the internal phase. Typically, the capsules arethemselves held within a polymeric binder to form a coherent layerpositioned between two electrodes. The technologies described in thesepatents and applications include:

-   -   (a) Electrophoretic particles, fluids and fluid additives; see        for example U.S. Pat. Nos. 5,961,804; 6,017,584; 6,120,588;        6,120,839; 6,262,706; 6,262,833; 6,300,932; 6,323,989;        6,377,387; 6,515,649; 6,538,801; 6,580,545; 6,652,075;        6,693,620; 6,721,083; 6,727,881; 6,822,782; 6,870,661;        7,002,728; 7,038,655; 7,170,670; 7,180,649; 7,230,750;        7,230,751; 7,236,290; 7,247,379; 7,312,916; 7,375,875;        7,411,720; 7,532,388; 7,679,814; 7,746,544; 7,848,006;        7,903,319; 8,018,640; 8,115,729; 8,199,395; 8,270,064; and        8,305,341; and U.S. Patent Applications Publication Nos.        2005/0012980; 2008/0266245; 2009/0009852; 2009/0206499;        2009/0225398; 2010/0148385; 2010/0207073; and 2011/0012825;    -   (b) Capsules, binders and encapsulation processes; see for        example U.S. Pat. Nos. 6,922,276 and 7,411,719;    -   (c) Films and sub-assemblies containing electro-optic materials;        see for example U.S. Pat. Nos. 6,982,178 and 7,839,564;    -   (d) Backplanes, adhesive layers and other auxiliary layers and        methods used in displays; see for example U.S. Pat. Nos.        7,116,318 and 7,535,624;    -   (e) Color formation and color adjustment; see for example U.S.        Pat. Nos. 7,075,502 and 7,839,564;    -   (f) Methods for driving displays; see for example U.S. Pat. Nos.        7,012,600 and 7,453,445;    -   (g) Applications of displays; see for example U.S. Pat. Nos.        7,312,784 and 8,009,348.

Known electrophoretic media, both encapsulated and unencapsulated, canbe divided into two main types, referred to hereinafter for convenienceas “single particle” and “dual particle” respectively. A single particlemedium has only a single type of electrophoretic particle suspending ina colored fluid, at least one optical characteristic of which differsfrom that of the particles. (In referring to a single type of particle,we do not imply that all particles of the type are absolutely identical.For example, provided that all particles of the type possesssubstantially the same optical characteristic and a charge of the samepolarity, considerable variation in parameters such as particle size andelectrophoretic mobility can be tolerated without affecting the utilityof the medium.) The optical characteristic is typically color visible tothe human eye, but may, alternatively or in addition, be any one of moreof reflectivity, retroreflectivity, luminescence, fluorescence,phosphorescence, or color in the broader sense of meaning a differencein absorption or reflectance at non-visible wavelengths. When such amedium is placed between a pair of electrodes, at least one of which istransparent, depending upon the relative potentials of the twoelectrodes, the medium can display the optical characteristic of theparticles (when the particles are adjacent the electrode closer to theobserver, hereinafter called the “front” electrode) or the opticalcharacteristic of the fluid (when the particles are adjacent theelectrode remote from the observer, hereinafter called the “rear”electrode, so that the particles are hidden by the colored suspendingmedium).

A dual particle medium has two different types of particles differing inat least one optical characteristic and a fluid which may be uncoloredor colored, but which is typically uncolored. The two types of particlesdiffer in electrophoretic mobility; this difference in mobility may bein polarity (this type may hereinafter be referred to as an “oppositecharge dual particle” medium) and/or magnitude. When such a dualparticle medium is placed between the aforementioned pair of electrodes,depending upon the relative potentials of the two electrodes, the mediumcan display the optical characteristic of either set of particles,although the exact manner in which this is achieved differs dependingupon whether the difference in mobility is in polarity or only inmagnitude. For ease of illustration, consider an electrophoretic mediumin which one type of particles is black and the other type white. If thetwo types of particles differ in polarity (if, for example, the blackparticles are positively charged and the white particles negativelycharged), the particles will be attracted to the two differentelectrodes, so that if, for example, the front electrode is negativerelative to the rear electrode, the black particles will be attracted tothe front electrode and the white particles to the rear electrode, sothat the medium will appear black to the observer. Conversely, if thefront electrode is positive relative to the rear electrode, the whiteparticles will be attracted to the front electrode and the blackparticles to the rear electrode, so that the medium will appear white tothe observer.

If, however, the two types of particles have charges of the samepolarity, but differ in electrophoretic mobility (this type of mediummay hereinafter to referred to as a “same polarity dual particle”medium), both types of particles will be attracted to the sameelectrode, but one type will reach the electrode before the other, sothat the type facing the observer differs depending upon the electrodeto which the particles are attracted. For example suppose the previousillustration is modified so that both the black and white particles arepositively charged, but the black particles have the higherelectrophoretic mobility. If now the front electrode is negativerelative to the rear electrode, both the black and white particles willbe attracted to the front electrode, but the black particles, because oftheir higher mobility will reach it first, so that a layer of blackparticles will coat the front electrode and the medium will appear blackto the observer. Conversely, if the front electrode is positive relativeto the rear electrode, both the black and white particles will beattracted to the rear electrode, but the black particles, because oftheir higher mobility will reach it first, so that a layer of blackparticles will coat the rear electrode, leaving a layer of whiteparticles remote from the rear electrode and facing the observer, sothat the medium will appear white to the observer: note that this typeof dual particle medium requires that the suspending fluid besufficiently transparent to allow the layer of white particles remotefrom the rear electrode to be readily visible to the observer.Typically, the suspending fluid in such a display is not colored at all,but some color may be incorporated for the purpose of correcting anyundesirable tint in the white particles seen therethrough.

Both single and dual particle electrophoretic displays may be capable ofintermediate gray states having optical characteristics intermediate thetwo extreme optical states already described.

Some of the aforementioned patents and published applications discloseencapsulated electrophoretic media having three or more different typesof particles within each capsule. For purposes of the presentapplication, such multi-particle media are regarded as sub-species ofdual particle media.

Many of the aforementioned patents and applications recognize that thewalls surrounding the discrete microcapsules in an encapsulatedelectrophoretic medium could be replaced by a continuous phase, thusproducing a so-called polymer-dispersed electrophoretic display, inwhich the electrophoretic medium comprises a plurality of discretedroplets of an electrophoretic fluid and a continuous phase of apolymeric material, and that the discrete droplets of electrophoreticfluid within such a polymer-dispersed electrophoretic display may beregarded as capsules or microcapsules even though no discrete capsulemembrane is associated with each individual droplet; see for example,U.S. Pat. No. 6,866,760. Accordingly, for purposes of the presentapplication, such polymer-dispersed electrophoretic media are regardedas sub-species of encapsulated electrophoretic media.

A related type of electrophoretic display is a so-called “microcellelectrophoretic display”. In a microcell electrophoretic display, thecharged particles and the fluid are not encapsulated withinmicrocapsules but instead are retained within a plurality of cavitiesformed within a carrier medium, typically a polymeric film. See, forexample, U.S. Pat. Nos. 6,672,921 and 6,788,449, both assigned to SipixImaging, Inc.

Although electrophoretic media are often opaque (since, for example, inmany electrophoretic media, the particles substantially blocktransmission of visible light through the display) and operate in areflective mode, many electrophoretic displays can be made to operate ina so-called “shutter mode” in which one display state is substantiallyopaque and one is light-transmissive. See, for example, U.S. Pat. Nos.5,872,552; 6,130,774; 6,144,361; 6,172,798; 6,271,823; 6,225,971; and6,184,856. Dielectrophoretic displays, which are similar toelectrophoretic displays but rely upon variations in electric fieldstrength, can operate in a similar mode; see U.S. Pat. No. 4,418,346.Electrophoretic media operating in shutter mode may be useful inmulti-layer structures for full color displays; in such structures, atleast one layer adjacent the viewing surface of the display operates inshutter mode to expose or conceal a second layer more distant from theviewing surface.

An encapsulated electrophoretic display typically does not suffer fromthe clustering and settling failure mode of traditional electrophoreticdevices and provides further advantages, such as the ability to print orcoat the display on a wide variety of flexible and rigid substrates.(Use of the word “printing” is intended to include all forms of printingand coating, including, but without limitation: pre-metered coatingssuch as patch die coating, slot or extrusion coating, slide or cascadecoating, curtain coating; roll coating such as knife over roll coating,forward and reverse roll coating; gravure coating; dip coating; spraycoating; meniscus coating; spin coating; brush coating; air knifecoating; silk screen printing processes; electrostatic printingprocesses; thermal printing processes; ink jet printing processes;electrophoretic deposition (See U.S. Pat. No. 7,339,715); and othersimilar techniques.) Thus, the resulting display can be flexible.Further, because the display medium can be printed (using a variety ofmethods), the display itself can be made inexpensively. However, theservice life of encapsulated electrophoretic displays, of both thesingle and dual particle types, is still lower than is altogetherdesirable. It appears (although this invention is in no way limited byany theory as to such matters) that this service life is limited byfactors such as sticking of the electrophoretic particles to the capsulewall, and the tendency of particles to aggregate into clusters whichprevent the particles completing the movements necessary for switchingof the display between its optical states. In this regard, oppositecharge dual particle electrophoretic displays pose a particularlydifficult problem, since inherently oppositely charged particles inclose proximity to one another will be electrostatically attracted toeach other and will display a strong tendency to form stable aggregates.Experimentally, it has been found that if one attempts to produce ablack/white encapsulated display of this type using untreatedcommercially available titania and carbon black pigments, the displayeither does not switch at all or has a service life so short as to beundesirable for commercial purposes.

It has long been known that the physical properties and surfacecharacteristics of electrophoretic particles can be modified byadsorbing various materials on to the surfaces of the particles, orchemically bonding various materials to these surfaces. For example,U.S. Pat. No. 4,285,801 (Chiang) describes an electrophoretic displaycomposition in which the particles are coated with a highly fluorinatedpolymer, which acts as a dispersant, and which is stated to prevent theparticles from flocculating and to increase their electrophoreticsensitivity. U.S. Pat. No. 4,298,448 (Muller et al.) describes anelectrophoretic medium in which the particles are coated with an organicmaterial, such as a wax, which is solid at the operating temperature ofthe medium but which melts at a higher temperature. The coating servesto lower the density of the electrophoretic particles and is also statedto increase the uniformity of the charges thereon. U.S. Pat. No.4,891,245 describes a process for producing particles for use inelectrophoretic displays, wherein a heavy, solid pigment, preferred forits high contrast or refractive index properties, is coated with apolymeric material. This process significantly reduces the specificdensity of the resultant particle, and is stated to create particleswith smooth polymer surfaces that can be chosen for stability in a givenelectrophoretic carrier fluid, and possess acceptable electrophoreticcharacteristics. U.S. Pat. No. 4,680,103 (Beilin Solomon I et al.)describes a single particle electrophoretic display using inorganicpigment particles coated with an organosilane derivative containingquaternary ammonium groups; this coating is stated to provide quickrelease of the particles from the electrode adjacent the observer andresistance to agglomeration.

Later, it was found that simple coating of the electrophoretic particleswith the modifying material was not entirely satisfactory since a changein operating conditions might cause part or all of the modifyingmaterial to leave the surface of the particles, thereby causingundesirable changes in the electrophoretic properties of the particles;the modifying material might possibly deposit on other surfaces withinthe electrophoretic display, which could give rise to further problems.Accordingly, techniques have been developed for securing the modifyingmaterial to the surface of the particles.

For example, U.S. Pat. No. 5,783,614 (Chen et al.) describes anelectrophoretic display using diarylide yellow pigment particlesmodified with a polymer of pentafluorostyrene. The modified particlesare produced by forming a mixture of the unmodified particles, thepentafluorostyrene monomer and a free radical initiator, and heating andagitating this mixture so that the monomer polymerizes in situ on thesurface of the particles.

U.S. Pat. No. 5,914,806 (Gordon II et al.) describes electrophoreticparticle formed by reacting pigment particles with a pre-formed polymerso that the polymer becomes covalently bonded to the surface of theparticles. This process is of course restricted to pigments and polymershaving chemical properties which allow the necessary reaction to formthe covalent bond. Furthermore, a polymer with only a few sites capableof reacting with the particle material has difficulty in reacting withthe solid interface at the particle surface; this can be due to polymerchain conformation in solution, steric congestion at the particlesurface, or slow reactions between the polymer and the surface. Often,these problems restrict such reactions to short polymer chains, and suchshort chains typically only have a small effect on particle stability inelectrophoretic media.

It is also known to use, in electrophoretic displays, particlesconsisting essentially of polymer; if dark colored particles arerequired, the polymer particles can be stained with a heavy metal oxide.See, for example, U.S. Pat. Nos. 5,360,689; 5,498,674; and 6,117,368.Although forming the electrophoretic particles from a polymer allowsclose control over the chemical composition of the particles, suchpolymer particles usually have much lower opacity than particles formedfrom inorganic pigments.

The aforementioned U.S. Pat. No. 6,822,782 teaches that the stability ofelectrophoretic media can be improved by using as the electrophoreticparticles pigment particles having from about 1 to about 15 percent byweight of the pigment of a polymer chemically bonded to, or cross-linkedaround, the pigment particles. These polymer-coated pigment particlesare prepared by a process comprising (a) reacting the particle with areagent having a functional group capable of reacting with, and bondingto, the particle, and also having a polymerizable orpolymerization-initiating group, thereby causing the functional group toreact with the particle surface and attach the polymerizable groupthereto; and (b) reacting the product of step (a) with at least onemonomer or oligomer under conditions effective to cause reaction betweenthe polymerizable or polymerization-initiating group on the particle andthe at least one monomer or oligomer, thereby causing the formation ofpolymer bonded to the particle. The preferred reagents for use in step(a) (the so-called “surface functionalization” step) of this process aresilanes, especially trialkoxysilanes with polymerizable groups attached(e.g., 3-(trimethoxysilyl)propyl methacrylate; and(N-[3-(trimethoxysilyl)propyl]-N′-(4-vinylbenzyl)-ethylenediaminehydrochloride). The process using trialkoxysilanes in practice requiresa vacuum drying stage to condense the silanols formed on the surface ofthe particles and to fully anchor the polymer shell to the bare pigmentsurface. The method works very well, but can result in pigments whichare difficult to disperse to a consistent particle size after surfacefunctionalization and prior to the polymerization step. In addition, themethod may not be usable with certain organic pigments (the methodrelies upon the presence on the particle surface of hydroxyl or similargroups present on almost all inorganic pigments), and such organicpigments may be needed in full color electrophoretic displays.Furthermore, it has been found that it can be difficult to adjust thezeta potential of the coated pigment particles produced by this process;the zeta potentials of the coated pigments particles tend to beindependent of the type of charging agent used in the electrophoreticmedium, and the ability to control zeta potential may be important insecuring optimum optical states from electrophoretic media.

Accordingly, this invention seeks to provide alternative methods forsurface modification of pigments which can overcome the aforementioneddisadvantages of the silane-based process described in theaforementioned U.S. Pat. No. 6,822,782.

SUMMARY OF INVENTION

Accordingly, in one aspect this invention provides a (first) process fortreatment of pigment particles (especially inorganic pigment particles)by physi-sorption of a reagent comprising polymerizable groups on to thesurfaces of the pigment particles by treating the particle with asolution of a reagent having a polymerizable orpolymerization-initiating group, thereby causing the reagent to becomephysi-sorbed on to the particle surface such that the reagent will notdesorb from the particle surface when the particle is placed in ahydrocarbon medium. This process may further comprise reacting thepigment particle with the reagent physi-sorbed thereon with at least onemonomer or oligomer under conditions effective to cause reaction betweenthe polymerizable or polymerization-initiating group on the particle andthe at least one monomer or oligomer, thereby causing the formation ofpolymer on the particle. This process may hereinafter be called the“absorption” process of the invention.

In one form of this first process, the reagent may be dissolved in anionic solvent or solvent mixture, such as a water/ethanol mixture. Theprocess may include adjusting the pH of the solution of the reagent tocontrol the charge on the pigment particle, and choosing the reagent tophysi-sorb depending upon the charge on the particle. As is well knownto those skilled in pigment chemistry, the charge on many pigmentparticles in ionic liquids depends upon the pH of the liquid, theretypically being one pH (the isoelectric point) at which the particle isuncharged. Above the isoelectric point of the pigment, the pigment isnegatively charged and the reagent may contain a quaternary ammoniumsalt grouping (much in the way organo-clays are prepared), while belowthe isoelectric point, the positively charged pigment surface can bemodified by adsorption of reagents containing anionic functional groups.Reagents with quaternary ammonium salt groupings include:[3-(methacryloyloxy)ethyl]trimethylammonium chloride (MAETAC),[3-(methacryloyloxy)ethyl]trimethylammonium methyl sulfate, and[3-(methacryloylamino)propyl]trimethylammonium chloride. Reagents withanionic functional groups include 3-sulfopropyl methacrylate potassiumsalt (SPMK) and sodium 4-vinylbenzenesulfonate. The process is notrestricted to pigments having inorganic oxide surfaces, and in principlemay be extended to any pigments which can be charged sufficiently topromote adsorption of the functionalizing reagent. The reagent which isphysi-sorbed on to the surface of the pigment particle should desirablybe chosen so that it becomes essentially irreversibly bound to theparticle in the low dielectric constant solvents (typically aliphatichydrocarbons) used in the polymerization step and in the internal phaseof the final electrophoretic display.

In another aspect, this invention provides a (second) process fortreatment of pigment particles (which may be organic or inorganicpigment particles) bearing nucleophilic groups (for example, aminegroups) on their surfaces by treatment of the pigment particles with areagent having a polymerizable or polymerization-initiating group, andalso comprising at least one electrophilic group. The electrophilicgroups on the reagent react with the nucleophilic groups on the particlesurfaces, thus attaching the polymerizable or polymerization-initiatinggroups to the particle surface. This process may further comprisereacting the pigment particle with the polymerizable orpolymerization-initiating groups thereon with at least one monomer oroligomer under conditions effective to cause reaction between thepolymerizable or polymerization-initiating group on the particle and theat least one monomer or oligomer, thereby causing the formation ofpolymer on the particle. This process may hereinafter be called the“nucleophilic” process of the invention.

The second process of the invention does not require a stronglynucleophilic group on the pigment particle, and may be used with organicpigments containing a nitrogenous ring, even when the nitrogen is notstrongly basic. For example, the second process is useful withquinacridone dyes such as dimethyl quinacridone (IUPAC:5,12-dihydro-3,10-dimethyl-quino[2,3-b]acridine-7,14-dione).

Reagents useful in this process include acid halides, such as4-vinylbenzyl chloride and methacryloyl chloride, and 2-isocyanatoethylmethacrylate. Both benzylic halides and acid chlorides are very reactivewith respect to nucleophilic substitution reactions. For example, thecoupling reaction with 4-vinylbenzyl chloride results in a styrene grouptethered to the surface.

The invention also provides a third process which is essentially avariant of the second process. Again, pigment particles (especiallyinorganic pigment particles) bearing nucleophilic groups on theirsurfaces are treated with a reagent having an electrophilic group butnot bearing a polymerizable or polymerization-initiating group so that aresidue of the reagent is chemically bonded to the pigment particle. Thereagent is chosen so that the treatment of the pigment particletherewith affects the zeta potential of the pigment particle. Thepreferred reagents for use in this process are alkyl halides, especiallybenzyl chloride or bromide; these alkyl halides are especially usefulfor treating titania particles. Treatment with either benzyl chloride orbromide shifts the zeta potential of the pigment particle to morepositive values.

The third process of the present invention can be carried out on pigmentparticles which have been silane-treated or had polymer formed thereonby any of the processes described in the aforementioned U.S. Pat. No.6,822,782, or by the first or second processes of the present invention.Thus, the third process of the invention is easily adopted andbeneficial because it does not require change in the functionalizationor polymer-forming reactions on the pigment. It is believed (althoughthe invention is in no way limited by this belief) that the thirdprocess of the invention serves to passivate the pigment surface(especially the inorganic, high energy metal oxide surface of manypigments used in electrophoretic displays) by covalent surfacefunctionalization with an alkyl chain. Accordingly, the third process ofthe invention may hereinafter be referred to as the “passivationprocess” of the present invention.

This invention extends to an electrophoretic material comprising aplurality of electrically charged particles disposed in a fluid andcapable of moving through the fluid under the influence of an electricfield, wherein at least one of the particles is produced by a process ofthe present invention. The electrically charged particles and the fluidmay be confined within a plurality of capsules or microcells.Alternatively, the electrically charged particles and the fluid may bepresent as a plurality of discrete droplets surrounded by a continuousphase comprising a polymeric material. The fluid may be liquid orgaseous. The invention also extends to an electrophoretic displaycomprising a layer of an electrophoretic material of the presentinvention and at least one electrode arranged to apply an electric fieldto the layer of electrophoretic material.

The displays of the present invention may be used in any application inwhich prior art electro-optic displays have been used. Thus, forexample, the present displays may be used in electronic book readers,portable computers, tablet computers, cellular telephones, smart cards,signs, watches, shelf labels, variable transmission windows and flashdrives.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 of the accompanying drawings is a graph showing the variation ofzeta potential with amount of charge control agent in experimentsdescribed in Example 6 below.

FIG. 2 is a reaction scheme of a passivation process of the presentinvention.

FIG. 3 is a graph, generally similar to that of FIG. 1, showing thevariation of zeta potential with amount of charge control agent inexperiments described in Example 8 below.

DETAILED DESCRIPTION

As indicated above, the present invention provides three differentprocesses for treatment of pigment particles. Although these processeswill mainly be described separately below, as already indicated, morethan one process of the invention may be used in the synthesis of asingle pigment particle; for example, a pigment particle which has beenfunctionalized using either the first or second process of the inventionmay, before or after formation of polymer on the functionalized pigment,be treated with the third process of the invention.

Part A: Absorption Process of the Invention

As already mentioned, the absorption process of the present inventionprovides a process for treatment of pigment particles by physi-sorptionof a reagent comprising polymerizable groups on to the surfaces of thepigment particles by treating the particle with a solution of a reagenthaving a polymerizable or polymerization-initiating group, therebycausing the reagent to become physi-sorbed on to the particle surfacesuch that the reagent will not desorb from the particle surface when theparticle is placed in a hydrocarbon medium. The absorption processavoids the vacuum drying step which, as previously mentioned, isnormally required when pigment particles are functionalized withsilanes, and provides a different surface chemistry which may lead tothe ability to obtain pigments in zeta potential ranges which cannot beachieved by the processes described in the aforementioned U.S. Pat. No.6,822,782. Elimination of the vacuum drying step is expected to improvethe dispersion of the pigment at the polymerization stage and therebyreduce large aggregates in the resulting polymer-coated product.Experimentally it has been found that when the absorption process of thepresent invention is applied to a commercial silica/alumina coatedtitania, the proportion of polymer in the final polymer-coated pigment(as measured by thermogravimetric analysis) is similar to that isachieved after a silane functionalization, but the final polymer-coatedpigment charges positively in electrophoretic media. This perhaps mightbe expected for cationic forms of the absorption process, but somewhatsurprisingly has been found to be the case also for anionic forms.

The following Examples are now given, though by way of illustrationonly, to show details of particularly preferred reagents, conditions andtechniques used in the absorption process of the present invention.

Example 1 Surface Modification Using Anionic Modifying Agents

The pigment being treated was dispersed at approximately 25% (by weight)in ethanol, and dilute hydrochloric acid was added to ensure thesolution was well below the isoelectric point of the pigment.3-Sulfopropyl methacrylate potassium salt (SPMK) (about 50-100 mg foreach gram of pigment) was dissolved in water and added to the pigmentdispersion. The solution is allowed to mix for several hours, thencentrifuged and the solid residue washed twice with ethanol. Theresulting pigment may be allowed to dry (this is not essential) and thendispersed into toluene for polymerization substantially as described inExample 28 of the aforementioned U.S. Pat. No. 6,822,782.

Example 2 Surface Modification Using Cationic Modifying Agents

The pigment being treated was dispersed at approximately 25% (by weight)in ethanol, and aqueous ammonia was added to ensure the solution waswell above the isoelectric point of the pigment.[3-(Methacryloyloxy)ethyl]trimethylammonium chloride (MAETAC) (about50-100 mg for each gram of pigment) was dissolved in water and added tothe pigment dispersion. The solution is allowed to mix for severalhours, then centrifuged and the solid residue washed twice with ethanol.The resulting pigment may be allowed to dry (this is not essential) andthen dispersed into toluene for polymerization substantially asdescribed in Example 28 of the aforementioned U.S. Pat. No. 6,822,782.If the pigment was not dried, a solvent switch procedure can be effectedto yield a pigment dispersion in toluene.

Example 3 Analysis of Various Pigments Produced by the AbsorptionProcess

Various pigments were treated by the absorption process of the inventionwith either SPMK or MAETAC as described in Examples 1 and 2 above, thenwashed, dispersed in toluene and a coating of poly(lauryl methacrylate)substantially as described in Example 28 of the aforementioned U.S. Pat.No. 6,822,782. The resultant polymer-coated pigments were tested bythermogravimetric analysis and suspended in Isopar E (a commercialhydrocarbon solvent) with the addition of 25 mg per gram of pigment ofSolsperse 17K (a charge control agent), and their zeta potentialsmeasured. The TGA values of the raw pigment, the functionalized pigmentand the polymer-coated pigment are shown in Table 1 below.

TABLE 1 Surface Notebook # Pigment Functionalization TGA_(raw) TGA_(sf)TGA_(poly) ζ(mV) 662-75-A Dupont R-794 MAETAC 1.187% 1.56% 4.95% +65.5662-74-A Dupont R-794 SPMK 1.187% 1.55% 6.78% +46.3 662-60 Shepherd Blue385 MAETAC 0.623% 2.01% 5.61% +85.8 662-72 Shepherd Blue 385 SPMK 0.623%1.46% 13.22%  +47.1 662-77 Shepherd Blue 30C591 MAETAC 0.476% 1.87%9.78% +80.3 662-76 Shepherd Blue 30C591 SPMK 0.476% 0.75% 9.03% +14.7662-61 Shepherd Green 260 MAETAC  0.07% 0.36% 1.44% +47

From the foregoing, it will be seen that functionalization of thepigments by the absorption process of the present invention producedfinal pigments have satisfactory amounts of polymer and good positivezeta potentials.

From the foregoing, it will be seen that the absorption process of thepresent invention can provide a simplification of the prior art silanefunctionalization process with elimination of a drying step. The processmay also result better reproducibility in terms of the average particlesize of the dispersion of functionalized pigment for the polymerizationstage. Both effects would be potential cost savers, the former throughprocess simplification, the latter by a potential yield increase.

Part B: Nucleophilic Process of the Invention

As already mentioned, the nucleophilic process of the present inventionprovides a process for treatment of pigment particles (which may beorganic or inorganic pigment particles) bearing nucleophilic groups ontheir surfaces by treatment of the pigment particles by with a reagenthaving a polymerizable or polymerization-initiating group, and alsocomprising at least one electrophilic group. The electrophilic groups onthe reagent react with the nucleophilic groups on the particle surfaces,thus attaching the polymerizable or polymerization-initiating groups tothe particle surface.

The nucleophilic process of the present invention can produce organicpigment particles which are readily dispersed in the hydrocarbon fluidstypically used in electrophoretic media. The process can also produceorganic and inorganic pigments having zeta potentials which aresubstantially independent of the charge control agents used, and thisconstant zeta potential may contribute to improved optical states inelectrophoretic displays.

The following Examples are now given, though by way of illustrationonly, to show details of particularly preferred reagents, conditions andtechniques used in the nucleophilic process of the present invention.

Example 4 Nucleophilic Process Using Dimethyl Quinacridone

Dimethyl quinacridone (Ink Jet Magenta E 02, 15 g) and toluene (135 g)were mixed and subjected to a high performance disperser for 1 minute.The resultant dispersion was transferred to a round-bottomed flaskequipped with a magnetic stir bar and the flask was placed into apreheated 42° C. silicone oil bath and placed under a nitrogenatmosphere. Triethylamine (12 mL, 86 mmole,) was added; after 1 hour4-vinylbenzyl chloride (VBC, 5.0 mL, 36 mmole) was added by syringe in asingle addition. The reaction mixture was then allowed to stir at 42° C.under a nitrogen atmosphere overnight.

The reaction mixture was poured into a plastic centrifuge bottle,diluted with toluene and centrifuged. The supernatant was decanted, thepigment washed with toluene, and the mixture again centrifuged. Thewashing procedure was repeated, then the supernatant was decanted andthe treated pigment dried in a 70° C. vacuum oven overnight.

Example 5 Polymer Coating of Pigment Produced by Nucleophilic Process

The dried pigment from Example 4 above was ground with a mortar andpestle. A sample was removed for TGA and the remaining pigment wasdispersed in toluene (10 wt % pigment dispersion) with sonication androlling. The resultant pigment dispersion was transferred to around-bottomed flask equipped with a magnetic stir bar and the flask wasplaced into a preheated 65° C. silicone oil bath. Lauryl methacrylate(20 g) was added to the reaction mixture, a Vigreux distilling columnwas attached as an air condenser, and the flask was purged with nitrogenfor at least 1 hour. A solution of 2,2′-azobis(2-methylpropionitrile)(AIBN) in toluene (0.20 g AIBN in 5 mL toluene) was syringed into thereaction flask all at once, and the reaction mixture was stirredvigorously at 65° C. overnight.

The reaction mixture was then poured into a centrifuge bottle, dilutedwith toluene and centrifuged for 30 minutes; the supernatant wasdecanted and submitted for GPC analysis. The pigment was washed oncewith toluene and centrifuged for 30 minutes, then the supernatant wasdecanted and the pigment was dried in a 70° C. vacuum oven overnight.

Example 6 Testing of Polymer Coated Pigment

The polymer-coated pigment produced in Example 5 above was ground with amortar and pestle, and it was dispersed to form a 20 wt % dispersion inIsopar E. This dispersion was sonicated and rolled for at least 24hours, then filtered through a fabric mesh to remove any largeparticles. A sample of the dispersion was removed and its percent solidmeasured, and the dry pigment from that measurement was submitted forTGA and density by pycnometer. The TGA value for the treated pigment was3.5%, whereas the raw pigment had a TGA value of 2.1%. The remainingdispersion was used to make 25 g of a 5% pigment dispersion with 0.5 gSolsperse 17000/g coated pigment for zeta potential measurement.

Samples of the dispersion thus prepared were mixed with varying amountsof Aluminum tris[3,5-di-tert-butylsalicylate], available commercially asBontron E88, a very acidic charge control agent, and the zeta potentialof the pigment measured. To provide controls, samples of the raw pigment(without the treatment with VBC and subsequent polymerization weresimilarly. The results are shown in FIG. 1 of the accompanying drawings.From the data in FIG. 1, it will be seen that the raw pigment exhibits asharp rise in zeta potential with concentration of the acidic chargecontrol agent, whereas the zero potential of the pigment produced by thenucleophilic process of the present invention is substantiallyinsensitive to concentration of charge control agent. Interestingly, thezeta potential of the pigment of the invention in OLOA 371 (a very basiccharge control agent) is essentially identical to that Solsperse, whenboth charge control agents were present in an amount of 0.5 g/g ofpigment; that is, the zeta potential of the pigment of the presentinvention is essentially the same in the presence of either a basic(OLOA) or acidic (Solsperse 17k/Bontron) charge control agent. Forcomparison, a white titania pigment (prepared substantially as describedin Example 28 of the aforementioned U.S. Pat. No. 6,822,782) dispersedwith OLOA was much more negative than under similar conditions in thepresence of Solsperse 17k, while the addition of small quantities ofBontron E88 had a dramatic effect on the zeta potential of this whitepigment, moving it in the more positive direction.

Example 7 Additional Pigments Produced by Nucleophilic Process of theInvention

Additional samples of Ink Jet Magenta E 02 and of other pigments werefunctionalized, polymer-coated and tested in the same manner as inExamples 4-6 above. The results are shown in Table 2 below, which alsoincludes data for the raw pigments.

TABLE 2 Zeta Average Amount potential particle Pigment CCA CCA (mV) size(nm) Inkjet Mag EO2 (invention) S17k  0.5 g/g 68.6 165 Inkjet Mag EO2(invention) S17k  0.5 g/g 72.4 177 Inkjet Mag EO2 (invention) S17k  0.5g/g 68.0 188 Inkjet Mag EO2 (invention) OLOA  0.5 g/g 84.5 203 InkjetMag EO2 (invention) OLOA  0.5 g/g 75.2 193 Inkjet Mag EO2 Raw S17k  0.5g/g 29.8 194 (control) Inkjet Yellow 4GC S17k 0.53 g/g −57.2 210(control) Inkjet Yellow 4GC S17k 0.54 g/g −10.3 100 (invention) InkjetYellow H4G S17k 0.54 g/g −27.5 230 (control) Inkjet Yellow H4G S17k 0.54g/g −14.6 205 (invention) PV Fast Yellow HG01 S17k 0.55 g/g 1.9 250(control) PV Fast Yellow HG01 S17k 0.54 g/g 10.9 162 (invention) TonerYellow HG (control) S17k 0.54 g/g −8.1 234 Toner Yellow HG S17k 0.54 g/g8.3 151 (invention)

From the foregoing, it will be seen that the nucleophilic process of thepresent invention provides a process capable of functionalizing a widevariety of pigments to enable the formation of polymer coatings thereon;the process is especially useful for attachment of a polymer shell toorganic pigments, which lack the silica or metal oxide surfaces commonto many inorganic pigments and capable of reacting with silanes. Theprocess is very simple and relies on well established chemistry in whichthe equilibrium strongly favors the coupled state so the yield of thenucleophilic reaction is essentially quantitative. The reagents used canbe selected to be very reactive species which react readily with evenweakly nucleophilic groups on the pigment particles. The nucleophilicgroups on the pigments particles can be either part of the actualcrystal structure of the pigment or can arise from an additive.

The ability of the nucleophilic process of the present invention to makethe zeta potential of the polymer-coated pigment essentially independentof the choice of charging agent (as demonstrated in the Examples above)provides great latitude in the development on new electrophoreticinternal phases, and has been shown to be of potential advantage interms of optical states accessible with typical driving voltages andpulse lengths.

Part C: Passivation Process of the Invention

As already mentioned, the passivation process of the present inventionprovides a process in which pigment particles bearing nucleophilicgroups on their surfaces are treated with a reagent having anelectrophilic group but not bearing a polymerizable orpolymerization-initiating group so that a residue of the reagent ischemically bonded to the pigment particle. The reagent is chosen so thatthe treatment of the pigment particle therewith affects the zetapotential of the pigment particle. The preferred reagents are typicallyalkyl halides (a term which is used herein to include aralkyl halides),especially benzyl chloride.

In prior art polymer-coated electrophoretic pigment particles which havebeen subjected to the silane/polymerization-treatment described above,in the final pigment particles the silane groups on the pigment particlesurface having been found to be the dominant moieties for generatingsurface charge and zeta potential of the pigment. Thus, modification ofpigment particle charging can be effected through incorporation offunctional silanes and/or by incorporation of functional monomers in thepolymer shell that change the inherent charge generation character of apigment. However, varying the charging of the pigment particles by thesetwo methods also affects other important pigment properties, such asdispersability in nonpolar solvents, polymer grafting density, andpigment dispersion viscosity. These highly interdependent propertiesmake it difficult to vary a pigment's zeta potential without affectingother important properties. Accordingly, to allow optimization ofvarious pigment properties independently of one another, it is desirableto synthesize a pigment with the appropriate silane and polymer shelland use post-polymerization modification of the pigment surface inaccordance with the passivation process of the present invention inorder to control zeta potential and thus electrophoretic mobility.

As already noted, the preferred reagents for use in the passivationprocess of the present invention are alkyl halides, especially benzylchloride, preferably in the presence of triethylamine, as illustrated inFIG. 2 of the accompanying drawings. Typically, the benzyl chlorideshould be used in an amount of about 30 molecules per square nanometerof pigment surface, which is estimated to be about a fivefold excessrelative to the nucleophilic hydroxyl groups available on a typicalmetal oxide pigment surface; the extent of benzylation may be inferredthrough the shift in the maximum zeta potential of the pigment. Pigmentzeta potential is typically determined in Isopar E with the chargecontrol agent Solsperse 17000; the zeta potential shift increases withincreasing reactivity for the alkylation reaction, and such increasedreactivity can be achieved through increasing the reaction temperatureor time, solvent polarity, and strength or hindrance of thenon-nucleophilic base. Typical positive zeta shift magnitudes range froma net +10 to +60 mV. Recommended alkylation conditions for reaction withbenzyl chloride are a slightly polar organic solvent (toluene ortetrahydrofuran) in the presence of a non-nucleophilic organic base(triethylamine or diisopropylethylamine) at about 66° C. The reactioncan be performed immediately treatment of the raw pigment with silane orafter polymer coating.

For example, in one series of experiments a raw silica/alumina coatedtitania pigment (R794 sold by du Pont) was found to have a weight lossof 1.08% during TGA. After treatment with vinylbenzylchloride (VBC, anelectrophile similar to benzyl chloride) in the presence oftriethylamine, the weight loss increased to 1.23%, corresponding to theaddition of 1.03 alkyl group per square nanometer of pigment surface.Subsequent polymerization of the VBC treated pigment with laurylmethacrylate increased weight loss to 3.90%. This subsequent grafting ofpolymer to the VBC-treated titania verifies the covalentsurface-functionalization of the metal oxide.

The passivation process of the present invention works through themodification of pigment zeta potential through covalent attachment ofalkyl (or other) groups to the pigment surface. The attachment of benzylgroups to the surface of white titania pigments with inherently negativezeta potential values before modification serves to shift the zetapotential to a more positive value. The functionality attached to theelectrophilic alkyl group will serve to determine the sign and magnitudeof the zeta potential modification. Using 4-fluorobenzylchloride or4-nitrobenzylchloride will tend to induce a more negative zeta potentialthrough fluorinated and acidic surface-functionalization. Conversely,alkylation with basic alkyl groups like 4-(chloromethyl)pyridine or4-(dimethylamino)benzoyl chloride would modify the zeta potential tomore robust positive values. Finally, incorporation of tert-butyl benzylchloride or long chain alkyl halides like 1-bromooctane could be usefulto provide additional steric hindrance to exclude diffusion of moleculesto the pigment surface.

The following Examples are now given, though by way of illustrationonly, to show details of particularly preferred reagents, conditions andtechniques used in the passivation process of the present invention.

Example 8 Passivation Process of the Invention Applied to Spinel-BasedBlack Pigment

This Example reports the results of preliminary experiments in which aspinel-based polymer-coated black pigment was treated with benzylchloride and benzyl bromide to test the hypothesis that amine groupspresent in the pigment could be quaternized and hence permanentlypositively charged, thus producing a pigment which is insensitive to thechoice of charging agent.

A polymer-coated black pigment based on Shepherd BK444 and producedsubstantially as described in Example 1 of U.S. Pat. No. 8,270,064 wastreated with benzyl chloride in substantially the same manner as inExample 4 above except that the reaction was conducted in Isopar E. Thepolymer-coated black pigment (24 g), benzyl chloride (4 g),triethylamine (4.7 g) and Isopar E were mixed at room temperature for 24hours. The resultant modified pigment was repeatedly centrifuged andwashed with Isopar E. Dispersions of the pigment were made with BontronE88 and variable amounts of OLOA 371, and their zeta potentialsmeasured. To provide controls, similar dispersions of the untreatedpolymer-coated black pigment were prepared and their zeta potentialsmeasured. The results are shown in FIG. 3.

From FIG. 3 it will be seen that the alkylated pigment is much lesssensitive to the presence of OLOA than the non-alkylated pigment andyields a nearly constant surface charge.

Example 9 Passivation Process of the Invention Applied to Titania-BasedWhite Pigments

Several titania-based white pigments were treated with benzyl chlorideeither after silane functionalization or after formation of polymer onthe pigment. Both the raw and the treated pigments were tested by TGA,and their maximum zeta potentials were measured in Isopar-E. The resultsare shown in Table 3 below.

The procedure used for treatment with benzyl chloride after formation ofa polymer layer on the white pigment was as follows. The pigment (300 g)was added to a 1 L plastic bottle to which tetrahydrofuran (THF—500 mL)was also added. The plastic bottle was rolled on a roll mill and thensonicated. The resultant dispersion was placed in a jacketed reactorequipped with a four-necked reactor top equipped with an overheadmechanical stirrer, a condenser capped with a nitrogen gas inlet, athermometer or thermocouple and a septum. The dispersion was rinsed intothe reactor with a small amount of THF and heated to reflux and stirredvigorously. The headspace of the reactor was purged with nitrogen andkept under positive pressure of nitrogen for the remaining stages of thereaction. Triethylamine was added by syringe to the reactor and theresultant mixture stirred for 30 minutes, then benzyl chloride was addedby syringe to the reactor, and the resultant reaction mixture stirredovernight at reflux. To isolate the product, the reactor was drainedinto two 1 L centrifuge bottles and the dispersion diluted to 1000 gtotal solvent and then centrifuged. The supernatant was decanted and thepigment redispersed by rolling with 1000 g total THF for 90 minute on aroll mill, after which the pigment dispersion was again centrifuged andthe supernatant decanted. The wet pigment pack was then dried at 70° C.overnight in a vacuum oven.

TABLE 3 Pigment Surface TGA/wash Zeta Potential No. Pigment BaseTreatment TGA Max 1 Essentially as U.S. Pat. No. 6,822,782, None1.98%/1.73% Nd Example 28, Part A 2 As Pigment 1 Benzyl chloride,1.87%/1.81% Nd triethylamine 3 As Pigment 2 after benzyl chloridePoly(lauryl 9.22%/9.16% −3.4 mV treatment methacrylate) 4 As Pigment 1(with process None 8.69%/7.87% −56 mV modifications) 5 As Pigment 4.BzCl, TEA 7.56%/7.91% −25 mV 6 Essentially as U.S. Pat. No. 8,582,196,None 8.93%/7.77% −91 mV Example 1 7 As Pigment 6 BzCl, TEA 7.43%/7.77%−52 mV 8 As Pigment 6 BzCl, TEA 7.63%/7.77% −11 mV

Following the various surface modifications, Pigments 6 and 7 wereconverted into experimental single pixel displays as described in U.S.Pat. No. 8,582,196, Example 2 using the same spinel-based black pigmentthere described, and the resultant experimental displays were subjectedto electro-optical tests as described in Example 3 of this patent. Theresults are shown in Table 4 below. Prior to the electro-optical tests,the single pixel displays were switched repeatedly to their extremeblack and white states, then finally switched to black or white, and theL* value measured 3 seconds after the end of the final drive pulse toallow transient effects to dissipate. The image stability figures aremeasured by allowing the display to remain in a black or white extremestate for a dwell time of 10 seconds, driving it to its opposite opticalstate, measuring the L* value of this state immediately (20milliseconds) after the end of the drive pulse and 30 seconds later, andtaking the difference. The DSD (dwell state dependency) values aresimilarly measured by allowing the display to remain in a black or whiteextreme state for a dwell time of 20 seconds, driving it to its oppositeoptical state, measuring the L* value of this state immediately afterthe end of the drive pulse and 30 seconds later, and taking thedifference.

TABLE 4 Formulation WS DS W:K Ratio White/Black Pigment L* WS L* DS WSis DS is DSD DSD wt % Pigment wt % 6 (no surface 73.9 21.2 0.0 −3.3 0.81.4 4.8:1 47.5% 39.25/8.2  treatment) 6 (no surface 75.1 22.3 0.0 −4.00.7 2.7 6.1:1 47.5% 40.8/6.7 treatment) 6 (no surface 73.3 25.8 0.1 −1.90.2 9.0 8.5:1 47.5% wt 42.5/5.0 treatment) 7 (BzCl surface 72.3 16.0 0.2−1.0 −0.3 2.9 4.8:1 47.5% 39.25/8.2  treatment) 7 (BzCl surface 73.918.0 0.1 −1.4 −0.5 5.1 6.1:1 47.5% 40.8/6.7 treatment) 7 (BzCl surface74.9 24.1 0.0 −2.2 0.1 5.0 8.5:1 47.5% 42.5/5.0 treatment)

From the data in Table 4, it will be seen that the benzyl chloridesurface treatment did not significantly affect the white state of thedisplays (the change following the benzyl chloride treatment is not morethan 1-2 L*) but did result in a substantial decrease (about 5 L*) inthe L* value of the dark state; thus, the benzyl chloride treatmentproduced a useful increase (about 3-4 L*) in the dynamic range of thedisplays. Statistical analysis indicates no significant changes in imagestability and DSD data between the untreated and the benzyl-treatedpigments. From the foregoing, it will be seen that the passivationprocess of the present invention allows surface functionalization ofpigment particles, and consequent modification of pigment zetapotential, through covalent attachment of alkyl groups to the pigmentsurface. Specifically, benzyl group attachment to the surface of whitepigments with inherently negative zeta potential values beforemodification serves to shift their zeta potential to a more positivevalue. Although this is demonstrated above for titania-based whitepigments, it may reasonably be assumed to apply to any inorganic pigmentwith a nucleophilic metal oxide surface. The sign and magnitude of thezeta potential modification may be controlled by functional groupsattached with an electrophilic alkyl group. For example, 4-fluorobenzylchloride and 4-nitrobenzyl chloride should induce a more negative zetapotential, since fluorinated and acidic surface-functionalization aredocumented to effect zeta potential modification of colloids in nonpolarliquids. Conversely, alkylation with basic alkyl groups such4-(chloromethyl)pyridine or 4-(dimethylamino)benzoyl chloride wouldserve to modify the zeta potential to more positive values. Finally,treatment with tert-butyl benzyl chloride or long chain alkyl halides,such as 1-bromooctane may be useful to provide additional sterichindrance to exclude diffusion of molecules to the pigment surface.

It will be apparent to those skilled in the art that numerous changesand modifications can be made in the specific embodiments of theinvention described above without departing from the scope of theinvention. Accordingly, the whole of the foregoing description is to beinterpreted in an illustrative and not in a limitative sense.

1. A process for treatment of pigment particles, the process comprisingphysi-sorping a reagent comprising polymerizable groups on to thesurfaces of the pigment particles by treating the particle with asolution of a reagent having a polymerizable orpolymerization-initiating group, thereby causing the reagent to becomephysi-sorbed on to the particle surface such that the reagent will notdesorb from the particle surface when the particle is placed in ahydrocarbon medium.
 2. A process according to claim 1 wherein thepigment particle comprises an inorganic pigment.
 3. A process accordingto claim 1 further comprising reacting the pigment particle with thereagent physi-sorbed thereon with at least one monomer or oligomer underconditions effective to cause reaction between the polymerizable orpolymerization-initiating group on the particle and the at least onemonomer or oligomer, thereby causing the formation of polymer on theparticle.
 4. A process according to claim 1 wherein the pigment isnegatively charged and the reagent contains a quaternary ammonium salt.5. A process according to claim 4 wherein the quaternary ammonium saltcomprises at least one of [3-(methacryloyloxy)ethyl]trimethylammoniumchloride, [3-(methacryloyloxy)ethyl]trimethylammonium methyl sulfate,and [3-(methacryloylamino)-propyl]trimethylammonium chloride.
 6. Aprocess according to claim 1 wherein the pigment is positively chargedand the reagent contains an anionic functional group.
 7. A processaccording to claim 6 wherein the reagent comprises at least one of3-sulfopropyl methacrylate potassium salt and sodium4-vinylbenzenesulfonate.
 8. A process for treatment of pigment particlesbearing nucleophilic groups on their surfaces, the process comprisingtreating the pigment particles with a reagent having a polymerizable orpolymerization-initiating group, and also comprising at least oneelectrophilic group under conditions which cause the electrophilicgroups on the reagent to react with the nucleophilic groups on theparticle surfaces, thus attaching the polymerizable orpolymerization-initiating groups to the particle surface.
 9. A processaccording to claim 8 further comprising reacting the pigment particlewith the polymerizable or polymerization-initiating groups thereon withat least one monomer or oligomer under conditions effective to causereaction between the polymerizable or polymerization-initiating group onthe particle and the at least one monomer or oligomer, thereby causingthe formation of polymer on the particle.
 10. A process according toclaim 8 wherein the pigment is an organic pigment containing anitrogenous ring.
 11. A process according to claim 10 wherein thepigment is a quinacridone dye.
 12. A process for treatment of pigmentparticles bearing nucleophilic groups on their surfaces, the processcomprising treating the pigment particles with a reagent having anelectrophilic group but not bearing a polymerizable orpolymerization-initiating group under conditions such that a residue ofthe reagent is chemically bonded to the pigment particle, the treatmentof the pigment particle with the reagent changing the zeta potential ofthe pigment particle.
 13. A process according to claim 12 wherein thereagent is an alkyl or aralkyl halide.
 14. A process according to claim12 wherein the pigment particles have previously been treated with asilane coupling agent.
 15. A process according to claim 14 wherein thepigment particles have previously been treated with a silane couplingagent and have had a polymer shell formed thereon.
 16. A processaccording to claim 12 wherein the pigment particle is treated with thereagent having the electrophilic group in the presence of a slightlypolar organic solvent in the presence of a non-nucleophilic organicbase.
 17. A process according to claim 16 wherein the slightly polarorganic solvent comprises at least one of toluene and tetrahydrofuran,and the non-nucleophilic organic base comprises at least one oftriethylamine and diisopropylethylamine.
 18. An electrophoretic materialcomprising a plurality of electrically charged particles disposed in afluid and capable of moving through the fluid under the influence of anelectric field, wherein at least one of the charged particles isproduced by the process of claim
 1. 19. An electrophoretic materialcomprising a plurality of electrically charged particles disposed in afluid and capable of moving through the fluid under the influence of anelectric field, wherein at least one of the charged particles isproduced by the process of claim
 8. 20. An electrophoretic materialcomprising a plurality of electrically charged particles disposed in afluid and capable of moving through the fluid under the influence of anelectric field, wherein at least one of the charged particles isproduced by the process of claim 12.